EP1202624B1 - Suspensions aqueuses de composes a faible solubilite dans l'eau - Google Patents

Suspensions aqueuses de composes a faible solubilite dans l'eau Download PDF

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Publication number
EP1202624B1
EP1202624B1 EP00948975A EP00948975A EP1202624B1 EP 1202624 B1 EP1202624 B1 EP 1202624B1 EP 00948975 A EP00948975 A EP 00948975A EP 00948975 A EP00948975 A EP 00948975A EP 1202624 B1 EP1202624 B1 EP 1202624B1
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Prior art keywords
aqueous suspension
low solubility
halogenated
preparation
solubility compound
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German (de)
English (en)
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EP1202624A1 (fr
EP1202624A4 (fr
Inventor
Alan M. Yeoman
Fredrick A. Grunewald
Jonathan N. Howarth
Alan D. Harrison
Brian R. Sook
Thomas Kruppa
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BWA Water Additives UK Ltd
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Great Lakes Chemical Corp
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
    • A01N43/70—Diamino—1,3,5—triazines with only one oxygen, sulfur or halogen atom or only one cyano, thiocyano (—SCN), cyanato (—OCN) or azido (—N3) group directly attached to a ring carbon atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/48—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —S—C≡N groups
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds

Definitions

  • the present invention relates generally to compounds such as biocides that have poor solubility and/or stability in water, and more particularly to methods and compositions for improving the stability and/or dissolution rate of such compounds.
  • Many compounds that have low solubility in water have other properties that make them particularly appropriate for use in aqueous systems.
  • many solid halogen donor materials such as halogenated hydantoins have low solubility, but are effective and economical biocides for recreational and industrial water systems.
  • non-biocides such as cyanuric acid have low solubility but are effective UV stabilizers for halogen source materials.
  • solid halohydantoins such as bromochlorodimethylhydantoin (BCDMH) have been used to sanitize waters for many years.
  • BCDMH bromochlorodimethylhydantoin
  • many solid halogen donors and all of the halohydantoins have low water solubility, slow dissolving kinetics and are hydrolytically unstable.
  • the water solubility for BCDMH for example, is low, approximately 1,500 mg/liter at 20°C, and it dissolves slowly, depending on surface area, contact time and water temperature.
  • dissolved BCDMH is not hydrolytically stable because it hydrolyses to yield dimethylhydantoin and the biocidal hypohalous acids, hypochlorous acid and hypobromous acid, which in turn degrade to the respective halides, chloride and bromide, within hours.
  • Solid halogen donors are available as solids in powdered form and also in various compressed forms such as granules, tablets or briquettes. These are dosed to treated water systems by several means, each of which is labor intensive and exposes workers to the solid product. Among the dosing methods are:
  • terbuthylazine [2-(tert-butylamino)-4-chloro-6-(ethylamino)-s-triazine]
  • oxidizing halogen More detail regarding this type of application may be found, for instance, in Impact of Cooling Water Treatment Trends on Algae Control by J. F. Kramer Off. Proc. -Int. Water Conf. (1995),56 th, 449-456.
  • the product is available as a 96% wettable powder (Bellacide® 320), as well as a 44.7% aqueous dispersion (Belclene® 329) and a 4% aqueous dispersion (Bellacide® 325).
  • the product brochure from FMC entitled Bellacide® 325 An Effective Algal control Agent Recommended for Recirculating Cooling Water Systems and Decorative Fountains recommends product addition at a point in the system where there is good mixing such as in the cooling tower sump near the recirculating pump.
  • BNEF 2-(2-bromo-2-nitro)-ethenyl furan
  • Isocyanuric Acid As to non-biocidal water additives with low solubility, Isocyanuric Acid (hereinafter "CYA,” and also referred to as S-triazine-2,4,6-trione), is used in water treatment to stabilize oxidizing halogen against decomposition.
  • CYA Isocyanuric Acid
  • S-triazine-2,4,6-trione S-triazine-2,4,6-trione
  • CYA solubility in water is approximately 2700 ppm at 20°C.
  • CYA is typically supplied as a 99% to 100% pure granular material.
  • CYA has uses as a chemical intermediate in the manufacture of resins, plastics additives and coatings. For the reasons noted above, it would be advantageous if easily pumped, rapidly dissolving concentrated aqueous formulations of CYA were available.
  • US-A-5 730 996 discloses a pesticide product containing an intercalated low water-soluble pesticide.
  • a method of improving the rate of dissolution in water of a low solubility compound comprising:
  • an aqueous suspension comprising 1% to 80% of a low solubility compound, 0.1 to 10% of a rheology additive, and water; wherein said rheology additive comprises platelets or particles that orient together with ionic or hydrogen bonds, and wherein said low solubility compound is present in an amount at least as great as the amount of rheology additive.
  • the invention may also provide an improvement in hydrolytic stability of the low solubility compound.
  • One object of the present invention is to provide improved methods for providing low solubility compounds to aqueous systems.
  • the present invention makes improved aqueous preparations of substances which exhibit one or more of the following characteristics:
  • the low solubility compound may be one having poor hydrolytic stability which limits storage life of the substance in aqueous preparations.
  • inventive preparations which may either be made on site or premanufactured, are thickened suspensions that exhibit one or more of the following improvements:
  • one aspect of the invention improves the performance of compounds that would be useful as water additives, but which have low solubility in water.
  • solubility in water of less than 1% is considered to be low solubility.
  • the present invention also improves the performance of low solubility water additives that have poor hydrolytic stability.
  • poor hydrolytic stability is indicated when the additive has a decomposition half-life of less than about seven (7) days.
  • bromochlorodimethylhydantoin BCDMH
  • bromonitroethenylfuran BNEF
  • bromonitrostyrene BNS
  • terbuthylazine TZ
  • cyanuric acid CYA
  • TCCA trichloroisocyanuric acid
  • DCCA dichloroisocyanuric acid
  • DCDMH dibromodimethylhydantoin
  • DCDMH dichlorodimethylhydantoin
  • DCMEH dichloromethylethylhydantoin
  • MTT methylene-bis-thiocyanate
  • solid metal hypohalites such as calcium hypochlorite. All of these compounds exhibit low solubility and/or a poor rate of dissolution in aqueous systems (possibly also with poor hydrolytic stability).
  • the amount of water additive present in the inventive aqueous suspension it will be appreciated by the art that the appropriate amount will depend on the specific additive being employed, and the desired use of that additive. In general terms though, amounts of between 1% and 80% may advantageously be used, with amounts between about 20% to about 60% being more preferred. In the most preferred embodiments, the additive preferably comprises about 40% of the aqueous suspension.
  • rheology additives that may be used in the present invention are natural clays such as smectite, synthetic clays such as synthetic smectite, natural aluminas, synthetic aluminas, natural silicas, synthetic silicas, and organic dispersants.
  • synthetic smectite e.g. , Laponite®, from Southern Clay Products
  • a natural smectite e.g. , Van Gel from R.T. Vanderbilt Company, Inc.
  • the rheology additives comprise platelets or particles that orient together with ionic or hydrogen bonds to form three-dimensional structures. This structure formation is reversible due to the relatively weak nature of the bonds, so that when the bonds are disrupted by shearing action the structure comes apart, but re-establishes when the composition is at rest.
  • the rheology additive consists essentially of such platelets or particles.
  • the preferred rheology additives are thixotropic. This is an additional benefit when it is desired to pump the compositions.
  • the suspension comprises about 0.1% to about 10% rheology additive. In the more preferred embodiments about 0.5% to about 5% rheology additive is used. Most preferably, about 1% to about 4% rheology additive is present in the aqueous suspension.
  • rheology additive is the natural smectite marketed under the trade name Van Gel by R.T. Vanderbilt Company, Inc.
  • Van Gel the rheology additive preferably comprises about 2% to about 4% of the aqueous suspension.
  • rheology additive is the synthetic smectite marketed under the trade name Laponite® by Southern Clay Products, Inc.
  • Laponite® the rheology additive preferably comprises about 0.5% to about 3% of the aqueous suspension.
  • rheology additive is the synthetic alumina marketed under the trade name Dispal® by the Vista Chemical Company.
  • Dispal® the rheology additive preferably comprises about 1% to about 5% of the aqueous suspension.
  • rheology additives is the fumed silica marketed under the trade name Cab-O-Sil by Cabot Corporation.
  • Cab-O-Sil the fumed silica marketed under the trade name Cab-O-Sil
  • the rheology additive preferably comprises about 0.1% to about 10% of the aqueous suspension.
  • rheology additives may be used in combination.
  • a synthetic smectite such as Laponite® may be combined with a synthetic alumina such as Dispal® to provide the desired rheology additive.
  • the selection of the rheology additive may also be made to optimize other performance characteristics such as the stability of the aqueous suspension when frozen and thawed.
  • natural smectite rheology additives such as Van Gel-O have been found to provide significant freeze/thaw stability to the aqueous suspensions of the present invention.
  • the dissolution rate of BromiCide® Powder (approximately 96% bromochlorodimethylhydantoin, BCDMH, available from BioLab, Inc.) was determined by analyzing filtered samples over time from a stirred BromiCide Powder/water preparation. The time required to dissolve 90% of the BCDMH was calculated from a fit of the data. The biocidal efficacy of dissolved BCDMH against bacteria was compared with sodium hypochlorite at similar free halogen concentrations.
  • the BCDMH assay of BromiCide Powder was determined by adding a known amount, approximately 0.1 grams of BromiCide Powder, into 80 milliliters of water, stirring vigorously with a magnetic stirrer for approximately two minutes followed by filtration through a 0.45 micron filter. The total oxidizing halogen content of this filtrate was determined after the addition of potassium iodide (KI) and acetic acid by potentiometric titration with standardized (0.10 N) sodium thiosulfate. The result of this titration was used to calculate the percent BCDMH present in BromiCide Powder.
  • KI potassium iodide
  • acetic acid standardized (0.10 N) sodium thiosulfate
  • BCDMH Powder Dissolution Rate Minutes 0.5 1.0 1.5 2.0 3.0 5.5 8.0 10.5 20.0 45.5 52.0 % Dissolved 11.1 17.0 21.7 25.8 31.8 40.9 51.0 57.2 74.4 89.7 91.8
  • 0.1, 0.3, 0.6 or 0.9 mg/l total halogen expressed as chlorine was established by dilution from freshly prepared (filtered) standardized stock solutions of either BCDMH Powder or NaOCl into phosphate buffered water (approximate pH of 7.5 as described in the method).
  • An inoculum was standardized to yield 2x10 8 organisms per ml.
  • One ml of the standardized inoculum was mixed into 199 ml of phosphate buffered water containing the desired dosage of biocide.
  • a preparation was made by mixing 417 grams of BromiCide Powder, 3 grams of monobasic potassium phosphate (KH 2 PO 4 ) into 580 grams of water using a high shear mixer (Caframo BDC 6015 mixer with a 3 inch High shear dispersing impeller operated at approximately 800 rpm.).
  • the assay of the resulting preparation was determined as described in Example 1 except that approximately 0.2 grams of the preparation is initially dissolved in the 80 ml of water rather than 0.1 grams of powder because the preparation is approximately 40% BCDMH.
  • % R elative A ctivity L oss ⁇ ( I nitial A ssay - C urrent A ssay)/( I nitial A ssay) ⁇ x100.
  • % R elative A ctivity L oss ⁇ ( I nitial A ssay - C urrent A ssay)/( I nitial A ssay) ⁇ x100.
  • a preparation with an Initial Assay of 40% BCDMH would have a 10% relative activity loss when the current assay was 36% BCDMH
  • Pumping performance was tested using a diaphragm metering pump in suction lift mode.
  • a 4 liter graduated cylinder containing approximately 4 kg of the preparation was placed on the floor.
  • a diaphragm pump (pump model - Alpha 080NP6060D0, available from ProMinent Fluid Controls Inc.) was mounted 4 feet (122 cm) above the floor with the semi-rigid tubing from the suction side of the pump inserted into the preparation. The pump was discharged into a 4 liter beaker. Pumping performance was poor. Pumping dewatered and thickened the material in the graduated cylinder to the point where it would no longer pump.
  • This preparation dissolved more rapidly than dry BCDMH powder probably because of pre-wetting. This preparation was not a stable suspension, the shelf life as measured by accelerated storage testing was poor and suction lift pumping caused dewatering.
  • a preparation was made by mixing 417 grams of BromiCide Powder, 4 grams of boric acid (H 3 BO 3 ) and 10 grams of the Laponite® RD (available from Southern Clay Products), a synthetic hectorite clay thickening and suspending agent, with 569 grams of water using a high shear mixer as described in Example 2.
  • Accelerated storage stability was determined for this preparation as described in Example 2.
  • the relative activity loss was 12.0% at 15 days and 17.7% at 30 days. This represents a significant improvement over wetted powder at the 15 day point with a more modest improvement at 30 days.
  • a preparation was made by mixing 417 grams of BromiCide Powder, 3 grams of monobasic potassium phosphate (KH 2 PO 4 ) and 30 grams of the Dispal® 23N4-80 (available from Condea-Vista), a synthetic alumina thickening and suspending agent, with 550 grams of water using a high shear mixer as described in Example 2.
  • KH 2 PO 4 monobasic potassium phosphate
  • Dispal® 23N4-80 available from Condea-Vista
  • a preparation was made by mixing 417 grams of BromiCide Powder, 3 grams of monobasic potassium phosphate (KH 2 PO 4 ), 3 grams of the Laponite® RD and 9 grams of Laponite® RDS (both synthetic hectorite clay thickening and suspending agents available from Southern Clay Products), and 10 grams of Dispal® 23N4-80 (a synthetic alumina thickening and dispersing agent available from Condea-Vista) with 558 grams of water using a high shear mixer as described in Example 2.
  • KH 2 PO 4 monobasic potassium phosphate
  • Laponite® RD both synthetic hectorite clay thickening and suspending agents available from Southern Clay Products
  • Dispal® 23N4-80 a synthetic alumina thickening and dispersing agent available from Condea-Vista
  • biocidal efficacy was essentially the same as when predissolved BCMDH was used. This indicates that the dispersing and thickening agents are not inhibiting the release of BCDMH when diluted to use level.
  • This combination of synthetic clay and synthetic alumina from the previous examples showed that, at this level, the alumina did not negatively effect the superior dissolution rate associated with the synthetic clay only formula from Example 3. The addition of the alumina at this lower level did not significantly improve the accelerated storage stability of the preparation.
  • the dissolution rate, accelerated storage stability and biocidal efficacy of a 40% BCDMH preparation was determined.
  • the method was similar to that of Example 5 except that dimethylhydantoin (DMH) was added in an attempt to improve accelerated storage stability performance.
  • DMH dimethylhydantoin
  • a preparation was made by mixing 417 grams of BromiCide Powder, 3 grams of monobasic potassium phosphate (KH 2 PO 4 ), 3 grams of the Laponite® RD and 9 grams of Laponite® RDS (both synthetic hectorite clay thickening and suspending agents available from Southern Clay Products), 10 grams of Dispal® 23N4-80 (a synthetic alumina thickening and dispersing agent available from Condea-Vista) and 100 grams of dimethylhydantoin (DMH) (available from BioLab Inc.) with 458 grams of water using a high shear mixer as described in Example 2. This preparation has a very thick consistency.
  • KH 2 PO 4 monobasic potassium phosphate
  • Laponite® RD both synthetic hectorite clay thickening and suspending agents available from Southern Clay Products
  • Dispal® 23N4-80 a synthetic alumina thickening and dispersing agent available from Condea-Vista
  • DMH dimethylhydantoin
  • the dissolution rate, accelerated storage stability and biocidal efficacy of a 40% BCDMH preparation was determined.
  • the method was similar to that of Example 5 except that the synthetic alumina level was increased in an attempt to improve accelerated storage stability performance.
  • a preparation was made by mixing 417 grams of BromiCide Powder, 3 grams of monobasic potassium phosphate (KH 2 PO 4 ), 3 grams of the Laponite® RD and 9 grams of Laponite® RDS (both synthetic hectorite clay thickening and suspending agents available from Southern Clay Products), and 30 grams of Dispal® 23N4-80 (a synthetic alumina thickening and dispersing agent available from Condea-Vista) with 538 grams of water using a high shear mixer as described in Example 2.
  • KH 2 PO 4 monobasic potassium phosphate
  • Laponite® RD both synthetic hectorite clay thickening and suspending agents available from Southern Clay Products
  • Dispal® 23N4-80 a synthetic alumina thickening and dispersing agent available from Condea-Vista
  • the additional synthetic alumina did not improve accelerated storage stability performance compared to the preparation from Example 5.
  • the dissolution rate was slower than when either the synthetic clay or the synthetic alumina were used alone, approximately the same as wetted powder form Example 2. This behavior did not appear to effect BCDMH release at use level determined by measuring biocidal efficacy. As shown in Table 5, performance was equivalent to preparations from Examples 5 and 6 and very similar to dissolved BCMDH Powder.
  • a preparation was made by mixing 417 grams of BromiCide Powder, 3 grams of monobasic potassium phosphate (KH 2 PO 4 ) and 40 grams of the Van-Gel-O (available from Vanderbilt), a natural smectite clay thickening and suspending agent, with 540 grams of water using a high shear mixer as described in Example 2.
  • This preparation gave excellent pumping results, with consistent flow and no separation indicating very good dispersion stability.
  • This preparation exhibited excellent performance in the accelerated storage stability test, superior to the alumina only preparation described in Example 4.
  • the dissolution rate was slower than the wetted powder from Example 2 indicating that the clay is not inhibiting the release of BCDMH on dilution.
  • the dissolution rate, accelerated storage stability and ease of pumping a 40% BCDMH preparation were determined. This preparation was similar to the preparation described in Example 8 except that the natural clay level was decreased in an attempt to improve dissolution rate performance.
  • a preparation was made by mixing 417 grams of BromiCide Powder, 3 grams of monobasic potassium phosphate (KH 2 PO 4 ) and 30 grams of the Van-Gel-O (available from Vanderbilt), a natural smectite clay thickening and suspending agent, with 550 grams of water using a high shear mixer as described in Example 2.
  • KH 2 PO 4 monobasic potassium phosphate
  • Van-Gel-O available from Vanderbilt
  • the 47,000 gallon capacity system was continuously treated for several years with BromiCide® Tablets (approximately 96% BCMDH, available from BioLab, Inc.) using a bypass feeder at a use rate of approximately 160 pounds of tablets per week. This yielded an average free halogen residual of 0.19 ppm (expressed as Cl 2 ) with a measured range of 0.12 to 0.34 ppm (expressed as Cl 2 ). Adjusting the flow of system water through the bypass feeder and maintaining the level of tablets in the bypass feeder controlled the feed rate. The water flow rate varied between two and three gallons per minute depending on temperature and tablet bed level. For consistent control, the bypass feeder was filled several times per week. The actual usage rate during the monitoring period was 157 to 163 pounds of tablets per week.
  • This system was then treated with the preparation described in Example 9 by pumping product, in suction lift mode, from a 55 gallon drum into the system using a diaphragm pump (pump model - Alpha 080NP6060D0, available from ProMinent Fluid Controls Inc.).
  • the product discharged from the pump was mixed with one gallon per minute of system water using an in-line mixer (motionless mixer model number 3 ⁇ 4-80-4-6-2, available from Koflo Corporation).
  • the product feed rate was controlled by pump rate adjustment (set to 0.8 gallons per hour, specific gravity is 1.2) along with an interval timer (set for 3 minutes on and 7 minutes off). This feed rate is equivalent to 161.5 pounds of BCDMH fed per week. This yielded an average free halogen residual of 0.21 ppm (expressed as Cl 2 ) with a measured range of 0.13 to 0.25 ppm (expressed as Cl 2 ).
  • the dissolution rate, accelerated storage stability and biocidal efficacy of a terbuthylazine preparation was determined.
  • the method was similar to that of Example 7 except that the dispersed agent was terbuthylazine rather than BCDMH.
  • a preparation was made by mixing 417 grams of Bellacide® 320 (96% terbuthylazine, available from FMC Corporation), 3 grams of monobasic potassium phosphate (KH 2 PO 4 ), 3 grams of the Laponite® RD and 9 grams of Laponite® RDS (both synthetic hectorite clay thickening and suspending agents available from Southern Clay Products), and 30 grams of Dispal® 23N4-80 (a synthetic alumina thickening and dispersing agent available from Condea-Vista) with 538 grams of water using a high shear mixer as described in Example 2.
  • Bellacide® 320 96% terbuthylazine, available from FMC Corporation
  • KH 2 PO 4 monobasic potassium phosphate
  • Laponite® RD both synthetic hectorite clay thickening and suspending agents available from Southern Clay Products
  • Dispal® 23N4-80 a synthetic alumina thickening and dispersing agent available from Condea-Vista
  • the dissolution rate of terbuthylazine was determined as described in Examples 1 and 2 except that the target nominal solution concentration was 4 ppm terbuthylazine rather than the 400 ppm BCDMH.
  • Terbuthylazine concentrations were determined by HPLC.
  • Terbuthylazine dissolution rates are reported in Table 6 for Bellacide 320 powder, Bellacide® 325 liquid (a 4% aqueous terbuthylazine dispersion available from FMC Corporation) and this preparation. 90% dissolution was achieved in approximately 21 hours for powder. 31 ⁇ 2 hours for Bellacide® 325 and a little more than 2 hours for the preparation described in this example. The data fit was fair for powder and good for Bellacide® 325 and the preparation from this example.
  • Accelerated storage stability was determined for this preparation as described in Example 2 except that the active ingredient was determined by HPLC.
  • the relative activity loss was 3.2% at 30 days. This result is consistent with the good hydrolytic stability associated with terbuthylazine.
  • the algicidal efficacy was determined for Terbuthylazine in the form of Bellacide 320 powder.
  • Bellacide 325 and the preparation described in this example A test culture of Chlorella pyrenoidosa was prepared by incubating cells in Allen's media with 16 hours of fluorescent light per day. Cells were counted and standardized such that they could be added to test flasks to achieve a level of 300.000 cells/ml to yield a light green color. The test flasks, prior to inoculation, contained Allen's media treated with the desired level of terbuthylazine from either Bellacide 320 powder. Bellacide 325 or the preparation described in this example.
  • This example demonstrates that different substances can realize similar benefits from formulation with the thickening and dispersing agents.
  • a preparation was made as described in Example 7 except that 40% terbuthylazine was substituted for 40% BCDMH.
  • the dissolution rate of this 40% preparation was superior to the 4% commercial liquid dispersion, Bellacide 325.
  • the efficacy of the active ingredient was not effected in this preparation.
  • the excellent accelerated storage stability was expected because terbuthylazine is hydrolytically stable.
  • the dissolution rate, accelerated storage stability and ease of pumping of a terbuthylazine preparation was determined.
  • the method was similar to Example 8 except that the dispersed agent was terbuthylazine rather than BCDMH.
  • a preparation was made by mixing 417 grams of Bellacide® 320 (96% terbuthylazine, available from FMC Corporation), 3 grams of monobasic potassium phosphate (KH 2 PO 4 ) and 40 grams of the Van-Gel-O (available from R. T. Vanderbilt Company Inc.), a natural smectite clay thickening and suspending agent, with 540 grams of water using a high shear mixer as described in Example 2.
  • the dissolution rate of the terbuthylazine in this preparation was determined as described in Example 11.
  • This preparation exhibited dissolution rates even faster than the preparation described in Example 11.
  • Example 12 The ease of pumping of a preparation similar to Example 12 was determined. The procedure was similar to that of Example 12 except that the level of dispersing and thickening agent was reduced from 4.0% to 3.0%.
  • a preparation was made by mixing 417 grams of Bellacide® 320 (96% terbuthylazine, available from FMC Corporation), 3 grams of monobasic potassium phosphate (KH 2 PO 4 ) and 30 grams of the Van-Gel-O (available from R. T. Vanderbilt Company Inc.), a natural smectite clay thickening and suspending agent, with 550 grams of water using a high shear mixer as described in Example 2.
  • Example 13 The ease of pumping of a preparation similar to Example 13 was determined.
  • the method was similar to that of Example 13 except that 1.0% of a fumed silica thickening and dispersing agent was used instead of 3.0% of a natural clay.
  • a preparation was made by mixing 417 grams of Bellacide® 320 (96% terbuthylazine, available from FMC Corporation), 3 grams of monobasic potassium phosphate (KH 2 PO 4 ) and 10 grams of Cabosil M-5 (available from Cabot Corporation, a fumed silica thickening and suspending agent), with 570 grams of water using a high shear mixer as described in Example 2.
  • Bellacide® 320 (96% terbuthylazine, available from FMC Corporation
  • KH 2 PO 4 monobasic potassium phosphate
  • Cabosil M-5 available from Cabot Corporation, a fumed silica thickening and suspending agent
  • Example 7 The dissolution rate, and accelerated storage stability of a preparation similar to Example 7 was determined.
  • the method was similar to that of Example 7 except that the dispersed agent was 2-(2-bromo-2-nitro)-ethenyl furan (BNEF) rather than BCDMH.
  • BNEF 2-(2-bromo-2-nitro)-ethenyl furan
  • a preparation was made by mixing 400 grams of BNEF solid which had been ground in a mortar and pestle (99% BNEF prepared as described in U.S. Patent 5,138.076), 3 grams of monobasic potassium phosphate (KH 2 PO 4 ), 3 grams of the Laponite® RD and 9 grams of Laponite® RDS (both synthetic hectorite clay thickening and suspending agents available from Southern Clay Products), and 30 grams of Dispal® 23N4-80 (a synthetic alumina thickening and dispersing agent available from Condea-Vista) with 555 grams of water using a high shear mixer as described in Example 2.
  • KH 2 PO 4 monobasic potassium phosphate
  • Laponite® RD both synthetic hectorite clay thickening and suspending agents available from Southern Clay Products
  • Dispal® 23N4-80 a synthetic alumina thickening and dispersing agent available from Condea-Vista
  • the dissolution rate of BNEF was determined as described in Examples 1 and 2 except that the target nominal solution concentration was 40 ppm BNEF rather than the 400 ppm BCDMH. Terbuthylazine concentrations were determined by HPLC. BNEF dissolution rates are shown in Graph 2 for BNEF solid which had been ground in a mortar and pestle (99% BNEF prepared as described in US Patent 5,138,076), a 10% solution of BNEF dissolved in the organic solvent, propylene carbonate, as described in US Patent 5,122,301 and the preparation described in this Example. 90% dissolution was not achieved in any of these tests probably because BNEF hydrolyzes in water at a rate which was similar to the dissolving rate. The solid did not dissolve as rapidly as either liquid formulation. The dissolution rate of the preparation described in this example was similar to, to slightly more rapid than, that of the organic solvent, based formulation. This equivalent dissolution rate was achieved without contaminating the waste system with organic solvent.
  • Accelerated storage stability was determined for this preparation as described in Example 2 except that the active ingredient was determined by HPLC.
  • the relative activity loss was 20% at 30 days. This is a higher than the 4.1% activity loss for the 10% solution of BNEF dissolved in the organic solvent, propylene carbonate, reported in US Patent 5,122,301. The activity loss is probably due to the rapid hydrolysis of BNEF in water.
  • Example 7 The dissolution rate, and accelerated storage stability of a preparation similar to Example 7 was determined.
  • the method was similar to that of Example 7 except that the dispersed agent was isocyanuric acid (CYA) rather than BCDMH.
  • CYA isocyanuric acid
  • a preparation was made by mixing 400 grams of CYA granules which had been ground in a mortar and pestle (100% Isocyanuric Acid granules [4 to 10 mesh particle size] from Delcal Inc.), 3 grams of monobasic potassium phosphate (KH 2 PO 4 ), 3 grams of the Laponite® RD and 9 grams of Laponite® RDS (both synthetic hectorite clay thickening and suspending agents available from Southern Clay Products), and 30 grams of Dispal® 23N4-80 (a synthetic alumina thickening and dispersing agent available from Condea-Vista) with 555 grams of water using a high shear mixer as described in Example 2.
  • CYA granules which had been ground in a mortar and pestle
  • KH 2 PO 4 monobasic potassium phosphate
  • Laponite® RD both synthetic hectorite clay thickening and suspending agents available from Southern Clay Products
  • Dispal® 23N4-80 a synthetic alumina thickening and dispersing
  • the dissolution rate of CYA was determined as described in Examples 1 and 2 with a target nominal solution concentration of 400 ppm CYA.
  • CYA concentrations were determined by HPLC.
  • CYA dissolution rates are reported in Table 7 for Isocyanuric Acid granules and this preparation. 90% dissolution was achieved in 35 minutes for granules and 5 minutes for the preparation described in this example. The data fit was good for both the granules and the preparation from this example.
  • Isocyanuric Acid Dissolution Rates, 400 ppm Nominal Concentration Isocyanuric Acid granules Preparation from Example 16 Time to 90% Dissolution (Minutes) 35 5 R 2 0.94 0.97
  • This example demonstrates that substances other than biocides can realize similar benefits from formulation with the thickening and dispersing agents.
  • a preparation was made as described in Example 7 except that 40% CYA was substituted for 40% BCDMH.
  • the dissolution rate of this 40% preparation was much more rapid than CYA in granular form.
  • the excellent accelerated storage stability was expected because terbuthylazine is hydrolytically stable.
  • Example 8 The dissolution rate and accelerated storage stability of a preparation similar to Example 8 was investigated.
  • the method was similar to that of Example 8 except that the dispersed agent was methyene-bis-thiocyanate rather than BCDMH.
  • a preparation is made by mixing 400 grams of methyene-bis-thiocyanate , 3 grams of monobasic potassium phosphate (KH 2 PO 4 ) and 40 grams of the Van-Gel-O (available from R. T. Vanderbilt Company Inc.), a natural smectite clay thickening and suspending agent, with 557 grams of water using a high shear mixer as described in Example 2.
  • KH 2 PO 4 monobasic potassium phosphate
  • Van-Gel-O available from R. T. Vanderbilt Company Inc.
  • the dissolution rate of the methyene-bis-thiocyanate in this preparation is determined as described in Example 11, and is found to be significantly faster than the dissolution rate of the base compound.
  • Accelerated storage stability is determined for this preparation as described in Example 11.
  • the composition displays good hydrolytic stability.
  • Example 8 The dissolution rate and accelerated storage stability of a preparation similar to Example 8 was investigated.
  • the method was similar to that of Example 8. except that the dispersed agent was bromonitrostyrene rather than BCDMH.
  • a preparation is made by mixing 400 grams of bromonitrostyrene, 3 grams of monobasic potassium phosphate (KH 2 PO 4 ) and 40 grams of the Van-Gel-O (available from R. T. Vanderbilt Company Inc.), a natural smectite clay thickening and suspending agent, with 557 grams of water using a high shear mixer as described in Example 2.
  • KH 2 PO 4 monobasic potassium phosphate
  • Van-Gel-O available from R. T. Vanderbilt Company Inc.
  • the dissolution rate of the bromonitrostyrene in this preparation is determined as described in Example 11, and is found to be significantly faster than the dissolution rate of the base compound.
  • Accelerated storage stability is determined for this preparation as described in Example 11.
  • the composition displays good hydrolytic stability.
  • Example 8 The dissolution rate and accelerated storage stability of a preparation similar to Example 8 was investigated.
  • the method was similar to that of Example 8, except that the dispersed agent was TCCA rather than BCDMH.
  • a preparation is made by mixing 400 grams of TCCA, 3 grams of monobasic potassium phosphate (KH 2 PO 4 ) and 40 grams of the Van-Gel-O (available from R. T. Vanderbilt Company Inc.), a natural smectite clay thickening and suspending agent, with 557 grams of water using a high shear mixer as described in Example 2.
  • KH 2 PO 4 monobasic potassium phosphate
  • Van-Gel-O available from R. T. Vanderbilt Company Inc.
  • the dissolution rate of the TCCA in this preparation is determined as described in Example 11, and is found to be significantly faster than the dissolution rate of the base compound.
  • Accelerated storage stability is determined for this preparation as described in Example 11.
  • the composition displays good hydrolytic stability.
  • Example 8 The dissolution rate and accelerated storage stability of a preparation similar to Example 8 was investigated.
  • the method was similar to that of Example 8, except that the dispersed agent was calcium hypochlorite instead of BCDMH.
  • a preparation is made by mixing 400 grams of calcium hypochlorite, 3 grams of monobasic potassium phosphate (KH 2 PO 4 ) and 40 grams of the Van-Gel-O (available from R. T. Vanderbilt Company Inc.), a natural smectite clay thickening and suspending agent, with 557 grams of water using a high shear mixer as described in Example 2.
  • KH 2 PO 4 monobasic potassium phosphate
  • Van-Gel-O available from R. T. Vanderbilt Company Inc.
  • the dissolution rate of the calcium hypochlorite in this preparation is determined as described in Example 11, and is found to be significantly faster than the dissolution rate of the base compound.
  • Accelerated storage stability is determined for this preparation as described in Example 11.
  • the composition displays good hydrolytic stability.
  • Example 8 The dissolution rate and accelerated storage stability of a preparation similar to Example 8 was investigated.
  • the method was similar to that of Example 8, except that the dispersed agent was dibromodimethylhydantoin rather than BCDMH.
  • a preparation is made by mixing 400 grams of dibromodimethylhydantoin, 3 grams of monobasic potassium phosphate (KH 2 PO 4 ) and 40 grams of the Van-Gel-O (available from R. T. Vanderbilt Company Inc.), a natural smectite clay thickening and suspending agent, with 557 grams of water using a high shear mixer as described in Example 2.
  • KH 2 PO 4 monobasic potassium phosphate
  • Van-Gel-O available from R. T. Vanderbilt Company Inc.
  • the dissolution rate of the dibromodimethylhydantoin in this preparation is determined as described in Example 11, and is found to be significantly faster than the dissolution rate of the base compound.
  • Accelerated storage stability is determined for this preparation as described in Example 11.
  • the composition displays good hydrolytic stability.

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Claims (58)

  1. Procédé d'amélioration de la vitesse de dissolution dans de l'eau d'un composé de faible solubilité, ledit procédé comprenant :
    (a) de combiner un composé de faible solubilité avec de l'eau et un additif modificateur de rhéologie pour former une suspension aqueuse comprenant 1 % à 80 % dudit composé de faible solubilité, dans laquelle ledit additif modificateur de rhéologie comprend des plaquettes ou des particules qui s'orientent avec des liaisons ioniques ou hydrogène pour former une structure tridimensionnelle et dans laquelle ledit composé de faible solubilité est présent en quantité au moins aussi grande que celle de l'additif modificateur de rhéologie et
    (b) d'ajouter ladite suspension à de l'eau et de laisser le composé de faible solubilité se dissoudre dans l'eau.
  2. Procédé de la revendication 1 dans lequel ladite étape consistant à combiner combine le composé de faible solubilité avec de l'eau et une quantité d'additif modificateur de rhéologie suffisante pour fournir 0,5 % à 5,0 % d'additif modificateur de rhéologie dans la suspension aqueuse.
  3. Procédé de la revendication 1 dans lequel ledit composé de faible solubilité comprend un élément choisi dans le groupe constitué des hydantoïnes halogénées, acides isocyanuriques halogénés, furanes halogénés, styrènes halogénés, s-triazines, acide cyanurique, hypohalogénites de métaux solides et thiocyanates de faible solubilité.
  4. Procédé de la revendication 3 dans lequel ledit composé de faible solubilité est une hydantoïne halogénée.
  5. Procédé de la revendication 4 dans lequel ladite hydantoïne halogénée est la BCDMH.
  6. Procédé de la revendication 4 dans lequel ladite hydantoïne halogénée est la DBDMH.
  7. Procédé de la revendication 4 dans lequel ladite hydantoïne halogénée est la DCDMH.
  8. Procédé de la revendication 4 dans lequel ladite hydantoïne halogénée est la DCMEH.
  9. Procédé de la revendication 3 dans lequel ledit composé de faible solubilité est un acide isocyanurique halogéné.
  10. Procédé de la revendication 3 dans lequel ledit acide isocyanurique halogéné est le TCCA.
  11. Procédé de la revendication 9 dans lequel ledit acide isocyanurique halogéné est le DCCA.
  12. Procédé de la revendication 3 dans lequel ledit composé de faible solubilité est un hypohalogénite de métal solide.
  13. Procédé de la revendication 3 dans lequel ledit hypohalogénite de métal solide est l'hypochlorite de calcium.
  14. Procédé de la revendication 1 dans lequel ledit composé de faible solubilité est un furane halogéné.
  15. Procédé de la revendication 14 dans lequel ledit furane halogéné est le BNEF.
  16. Procédé de la revendication 1 dans lequel ledit composé de faible solubilité est un styrène halogéné.
  17. Procédé de la revendication 16 dans lequel ledit styrène halogéné est le BNS.
  18. Procédé de la revendication 1 dans lequel ledit composé de faible solubilité est l'acide cyanurique.
  19. Procédé de la revendication 1 dans lequel ledit composé de faible solubilité est une s-triazine.
  20. Procédé de la revendication 12 dans lequel ladite s-triazine est la terbuthylazine.
  21. Procédé de la revendication 1 dans lequel ledit composé de faible solubilité est un thiocyanate.
  22. Procédé de la revendication 21 dans lequel ledit thiocyanate est le MBT.
  23. Procédé de la revendication 1 dans lequel ledit additif modificateur de rhéologie comprend une argile naturelle ou synthétique.
  24. Procédé de la revendication 23 dans lequel ladite argile naturelle ou synthétique comprend une smectite synthétique.
  25. Procédé de la revendication 23 dans lequel ladite argile naturelle ou synthétique comprend une smectite naturelle.
  26. Procédé de la revendication 1 dans lequel ledit additif modificateur de rhéologie comprend une silice naturelle ou synthétique.
  27. Procédé de la revendication 1 dans lequel ledit additif modificateur de rhéologie comprend une alumine naturelle ou synthétique.
  28. Procédé de la revendication 1 dans lequel ledit additif modificateur de rhéologie comprend un dispersant organique.
  29. Procédé de la revendication 1 dans lequel ladite suspension aqueuse comprend 10 % à 80 % dudit composé de faible solubilité et 0,1 % à 10 % dudit additif modificateur de rhéologie.
  30. Suspension aqueuse comprenant 1 % à 80 % d'un composé de faible solubilité, 0,1 à 10 % d'un additif modificateur de rhéologie et de l'eau, dans laquelle ledit additif modificateur de rhéologie comprend des plaquettes ou des particules qui s'orientent avec des liaisons ioniques ou hydrogène et dans laquelle ledit composé de faible solubilité est présent en quantité au moins aussi grande que la quantité d'additif modificateur de rhéologie.
  31. Suspension aqueuse de la revendication 30 dans laquelle ledit composé de faible solubilité comprend un élément choisi dans le groupe constitué des hydantoïnes halogénées, acides isocyanuriques halogénés, furanes halogénés, styrènes halogénés, s-triazines, acide cyanurique, hypohalogénites de métaux solides et thiocyanates de faible solubilité.
  32. Suspension aqueuse de la revendication 31 dans laquelle ledit composé de faible solubilité est une hydantoïne halogénée.
  33. Suspension aqueuse de la revendication 32 dans laquelle ladite hydantoïne halogénée est la BCDMH.
  34. Suspension aqueuse de la revendication 32 dans laquelle ladite hydantoïne halogénée est la DBDMH.
  35. Suspension aqueuse de la revendication 32 dans laquelle ladite hydantoïne halogénée est la DCDMH.
  36. Suspension aqueuse de la revendication 32 dans laquelle ladite hydantoïne halogénée est la DCMEH.
  37. Suspension aqueuse de la revendication 31 dans laquelle ledit composé de faible solubilité est un acide isocyanurique halogéné.
  38. Suspension aqueuse de la revendication 37 dans laquelle ledit acide isocyanurique halogéné est le TCCA.
  39. Suspension aqueuse de la revendication 37 dans laquelle ledit acide isocyanurique halogéné est le DCCA.
  40. Suspension aqueuse de la revendication 30 dans laquelle ledit composé de faible solubilité est une s-triazine.
  41. Suspension aqueuse de la revendication 40 dans laquelle ladite s-triazine est la terbuthylazine.
  42. Suspension aqueuse de la revendication 31 dans laquelle ledit composé de faible solubilité est un furane halogéné.
  43. Suspension aqueuse de la revendication 42 dans laquelle ledit furane halogéné est le BNEF.
  44. Suspension aqueuse de la revendication 31 dans laquelle ledit composé de faible solubilité est un styrène halogéné.
  45. Suspension aqueuse de la revendication 44 dans laquelle ledit styrène halogéné est le BNS.
  46. Suspension aqueuse de la revendication 31 dans laquelle ledit composé de faible solubilité est l'acide cyanurique.
  47. Suspension aqueuse de la revendication 31 dans laquelle ledit composé de faible solubilité est un hypohalogénite de métal solide.
  48. Suspension aqueuse de la revendication 47 dans laquelle ledit hypohalogénite de métal solide est l'hypochlorite de calcium.
  49. Suspension aqueuse de la revendication 31 dans laquelle ledit composé de faible solubilité est un thiocyanate.
  50. Suspension aqueuse de la revendication 49 dans laquelle ledit thiocyanate est le MBT.
  51. Suspension aqueuse de la revendication 30 dans laquelle ledit additif modificateur de rhéologie comprend une argile naturelle ou synthétique.
  52. Suspension aqueuse de la revendication 51 dans laquelle ladite argile naturelle ou synthétique comprend une smectite synthétique.
  53. Suspension aqueuse de la revendication 51 dans laquelle ladite argile naturelle ou synthétique comprend une smectite naturelle.
  54. Suspension aqueuse de la revendication 30 dans laquelle ledit additif modificateur de rhéologie comprend un dispersant organique.
  55. Suspension aqueuse de la revendication 30 dans laquelle ladite suspension comprend 10 % à 80 % dudit composé de faible solubilité et 0,1 % à 10 % dudit additif modificateur de rhéologie.
  56. Suspension aqueuse de la revendication 30 dans laquelle ledit additif modificateur de rhéologie comprend une silice naturelle ou synthétique.
  57. Suspension aqueuse de la revendication 56 dans laquelle ladite silice naturelle ou synthétique est une silice fumée.
  58. Suspension aqueuse de la revendication 30 dans laquelle ledit additif modificateur de rhéologie comprend une alumine naturelle ou synthétique.
EP00948975A 1999-07-29 2000-07-28 Suspensions aqueuses de composes a faible solubilite dans l'eau Expired - Lifetime EP1202624B1 (fr)

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US20070243264A1 (en) * 2006-04-18 2007-10-18 Aram Garabedian Thickened Dilute Hypochlorite
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ZA200200708B (en) 2003-09-23
EP1568276A3 (fr) 2006-06-14
EP1202624A1 (fr) 2002-05-08
WO2001008484A1 (fr) 2001-02-08
KR20020065887A (ko) 2002-08-14
CA2378815A1 (fr) 2001-02-08
JP2003523318A (ja) 2003-08-05
ES2240126T3 (es) 2005-10-16
EP1568276A2 (fr) 2005-08-31
DE60019124D1 (de) 2005-05-04
US6281169B1 (en) 2001-08-28
KR100752532B1 (ko) 2007-08-29
DE60019124T2 (de) 2006-02-09
EP1202624A4 (fr) 2002-12-04
ATE291842T1 (de) 2005-04-15
JP4160301B2 (ja) 2008-10-01
AU771835B2 (en) 2004-04-01
AU6239100A (en) 2001-02-19
CA2378815C (fr) 2009-10-13

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